Autoester-polyepoxide compositions



.plied by the other reactants.

W td5ta F m Drawing. pplication January 28, 1957 sem N tsasos 14 Claims. 01. 260-19) mThis"inventionrelates to new products and compositionsl resulting from the reaction of polyepoxides with autoestersof .aryloxy'acids and the modification of such compositions with condensates of aldehydes and amnioniaderivatives, or condensates "of aldehydes and phenols, in regulated proportions to produce valuable compositions usefulin the manufacture of varnishes, molding compositions,.adhesives, films. and molded articles. The invention includes initial reaction mixtures or compositions as well as intermediate and final reaction products andLmethods for their production.

It is an object of this invention to produce new compositions of matter from suitable proportions of aryloxy acid. autoes'ters and polyepoxides with or without modificatiori with aldehydecondensates, which compositions arezsuitable for use incoating compositions, molding compositions and adhesives.

Another :object of this invention is the production of reaction mixtures of the aforesaid epoxides and aryloxy acidaautoesters with or without aldehyde condensates which are capable of reaction on the applicationof heat to form infusible, insoluble products.

. Another object of a this invention is the production of newireaction mixtures, as described above, which are stable: at ordinary temperatures for long periods of time and which may be converted to insoluble, infusible products bytheapplication of heat with or without the addition ofcatalyst. y Another object of this invention is to provide ,for the production of co-conversion products of polyepoxides and aryloxy acid autoesters or said products modified with aldehyde condensates, with such co-conversion products being characterized by extreme hardness, flexibility, and

resistance to water, alkali, and organic solvents.

Other Objects of the invention will appear from the following more detailed description with particular reference to the illustrative examples.

In general, the polyepoxides contemplated for use with the aryloxy acid autoesters to prepare the compositions of this invention are compounds containing an average of more than one, up to about twenty epoxide groups, per molecule. Such compounds, free from functional groups other than epoxide, carboxyl, and hydroxyl groups,

are reactive with active hydrogen-containing groups such as the carboxyl groups supplied by the aryloxy acid autoesters herein contemplated. Typical epoxides which have been found to be operable are complex resinous polyepoxides, resinous polyepoxide polyesters, epoxidized natural oils, and simple aliphatic polyepoxides.

The reaction products of this invention are prepared by converting the epoxide groups with the aryloxy acid autoesters, which are derivatives of a bis(arylene)-substituted aliphatic acid and, if desired, modifying said compositions with aldehyde condensates. Conversion of the epoxide groups is efliected by active hydrogen present in the hydroxyl, carboxyl Or amino groups which may be sup- The aryloxy acid autoester's suitable for use in preparing the compositions of this invention are described in detail in the copending Greenlee application, Serial No. 514,377 filed June 9, 1955; They may be prepared by heating an aryloxy acid in the presence of acetic anhy dride as illustrated by the following: i a i O/ h I It is to be understood that the product of the illustraa tive reaction is only one of a mixture ofmatei ials actu j ally produced. Whenever both hydroxyl groups Olitjhfi Diphenolic Acid are esterified, a branched structure, rather than the illustrated linear configuration, would result. The invention embraces using autoesters containing any number of monomeric units. Thus in Equation I above; It may represent any integer greater than 1. In compof sitions where n is a value greater than about 15, the'auto ester is ordinarily diflicult to handle since the mass becomes insoluble, and infusible, and cannot be readily dis. solved.

Further valuable variations in the type of composition obtained may be effected by varying the number of carboxyl groups esterified, resulting in resinous polyhydric phenols containing a desired amount of unreacted carboxylic acid. Toillustrate this type of composition, the reaction between 2 molecules of 4,4-bis(4-hydroxyphenyl)pentanoic acid results in an essentially resinous triphenolic acid.

he bis (hydroxyaryDsubstituted acid contemplated for use herein should have two hydroxyaryl groups attached to a single carbon atom. The preparation of such an aryloxy acid is most conveniently carried. out by condensing a keto-acid with the desired phenol. Experience in the preparation of bisphenol and related compounds indicates that the carbonyl group of the keto-acid must be positioned next to a terminal methyl group in order to obtain satisfactory yields. Prior applications, Serial Nos. 464,607 and 489,300, filed October 25, 1954, and Februrary 18, 1955, respectively, disclose a number of illustrative compounds suitable for use as the aryloxy-sub stituted acid, and methods of preparing the same. These materials, which are referred to for convenience by the trademarks of S. C. Johnson & Son, Inc., as Diphenolic Acid or DPA, consist of the condensationproducts Offij keto-acid such as levulinic and phenol, substituted phegenated. The Diphenolic Acid derived from substituted phenols, such as the alkylated phenols, are sometimes more desirable than the products obtained from unsubstituted phenols since the alkyl groups provide better or ganic solvent solubility, flexibility and water resistance. parts had an acid value of 9.6 and a softening point However, the unsubstituted product is usually more readi- (Durfans ry method) of 124 ly purified.

The resinous polyhydric phenols are preparedby auto- EXAMPLE 2 esterification of up to one-half the phenolic hydroxyl 5 By h same procedure as i Example 1 a mixture of groups of Diphenolic Acid With the CaI'bOXYI g p f 2 86 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid and other molecules of Diphenolic Acid. Partial esterifica- 102 parts f ti nhydride was heated at l45-178 C. 601119 give Products having appreciable acid Values, Such for a period of 1 /2 hours. The temperature was then as that represented by H' above, may be carried out by i d t 220 C. over a period of hour and held at heating at tempfifatures of from undel C011- this temperature for a period of 2 hours reducing the ditions whereby water of esterification is readily removed. pressure to around 30 mm. during the last half-hour of The Water removal may be facilitated y bubbling inert reaction time. The product, amounting to 272- parts, had gas through the reaction mixture during esterification or a a id value of 44.7 and a softening point of 124 C. by azeotropic distillation with a hydrocarbon solvent.

Convenient methods of esterification of the phenolic hy- EXAMPLE 3 droxyl groups involve heating the Diphenolic Acid in the presence of acetic anhydride in an amount equivalent F flask PTOVlded Wlth a thermometer, a m to the extent of esterification desired. For example, if it chamcal aguator, and a reflux condenser attached t9 is'desired to autoesterify approximately one-half of the h Condenser thmugh a Watfil' f p Cone/1011 Ofdlscarboxyl groups, one-half mol of acetic anhydride per 0 hate plflced 3 P P Y YP Y mol of Diphenolic Acid should be used. If approximate- Paula-1101c acld- With contlmwus agltatlofl the p ly complete autoesterification of the carboxyl groups is mm was faised held at 200440 desired, at least 1 mol of acetic anhydride per mol of for a P i of 7 hours, collectmg water formed from Diphenolic Acid should be used. Where more than the cohdehsahoh by dlshnahhh mm the Water traph ui n amount f acetic anhydride is used in {the resulting product, amounting to 276 parts, had anacid process, a portion of the phenolic hydroxyl groups not Value of 993 and a Sofiemhg Pol-ht of esterified by the carboxyl group of the Diphenolic Acid Illustrative h f compositions which may are acetylated and the amount of active hydrogen availp y In this e tlon are the complex epoxide resins able for the reactions of this invention is correspondingwhlch are Polyetheh denvahves, Polyhydnc Phenols 1 reducei with such polyfunctional coupling agents as polyhalo- Examples I to I11 inclusive describe the preparation hydrihsi polyepoxides" epihalohydhhs- Thes? ofautoesters of Diphenolic Acid. Proportions expressed be y q -P, Y 2 P Y Y in these and subsequent examples refer to pal-ts by Weight hols having alternating ahphatrc chains and nuclei conunless therwise i di t d, nected to each other by ether linkages, containing terv minal epoxide groups and free from functional groups EXAMPLE 1 other than epoxide and hydroxyl groups. It should be understood that significant amounts of the monomeric A mixture of 286 parts of 4,4-bis(4-hydroxyphenyl)- reaction products are often present. This would be illuspentanoic acid and 102 parts of acetic anhydride in a trated by III to V below where n equals Zero. Prepara- 3-neck flask provided with a thermometer, a mechanition of these epoxide materials as well as illustrative excal agitator, and a reflux condenser was heated with conamples are described in US. Patents, 2,456,408,.2,503,- tmuous agitation at 148l70 C. for a period of 2 /2 726, 2,615,007, 2,615,008, 2,688,805, 2,668,807 and hours. With continued agitation and removal of the 2,698,315. Well known commercial examples of these acetic acid the temperature was gradually increased to resins are the Epon resins marketed by theShell Chemical 215 C. and held at 215-235 C. for a period of 7 Corporation. Illustrative of the preparation ofithese hours. During the last /2 hour of heating the pressure epoxide resins are the following reactions wherein the was reduced to around 30 mm. so as to remove the last difunctional coupling agent is used in varying molar traces of acetic acid. The product, amounting to 256 excessive amounts:

Polyhydrie phenol and an epihalohydrin bis(hydroxyphenyl)isopropylidene excess epichlorohydrin C V O C OH TL C CH; I III Polyhydrlc phe a p y poxide bls(hydroxyphenyl)isopropylidene excess butylene dioxide CH2CHCHOHCHz- O OOHQCHOHOHOHOHQLO V OCHzCHOHQHCHl C 1 OH Polyhydric phenol and a polyhalohydrin bis (hydroxyphenyliisopropylldene excess a-glycerol dichlorohydrin Q a o i oHmHoHP o oon,onoHoH; -o ocm nofli queous alkali p y 1 l o o y I C CH; Tl Oflg CH; V

As used in the above formulas, it indicates the degree of polymerization, and its value depends on the molar ratio of reactants. As can be seen from these formulas,

the complex epoxide resins used in this invention contain terminal epoxide groups, and alcoholic hydroxylgroups attached to the aliphatic portions of the resin, the latter being formed by the splitting of epoxide groups in the reaction of the same with phenolic hydroxyl groups. Ultimately the reaction with the phenolic hydroxyl groups of the polyhydric phenols is accomplished by means of epoxide groups formed from halohydrins by the loss of hydrogenandhalogen (generally as shown by the following equation: 1

. o Other ,epoxide compositions which may be used include the .polyepoxide polyesterswhich may be prepared by esterifying tetrahydrophthalic anhydride with a glycol and epoxidizing the product of the esterification reaction. In the preparation of theffpolyesters, tetrahydrophthalic acidmay also be used as vfvell'as the simple: esters of tetrahydrophthalic acid such as dimefthyl and diethyl esters. There is a tenden'cywith tertiary glycols for dehydration to occur under the conditions used for esterification so that generally the primary and secondary glycols are the most satisfactory in the polyester formation. Glycols which may be used in the preparation of this polyester composition comprise, ingeneral, those glycols having 2 hydroxyl groups attached to separate carbon atoms and free from functional groups which would interfere with the esterification or' epoxidation reactions. These glycols include such glycols as ethylene glycoljdiethylene glycol, triethylene glycol, tetramethylene glycol, propylene glycol, polyethylene glycol, neopentyl glycol, and hexamethylene glycol. Polyepoxide polyesters may be prepared from thesepolyesters by epoxidizing the unsaturated portions of the tetrahydrophthalic acid residues in the polyester composition. By properly proportioning reactants in the polyester formation and regulating the epoxidation reaction, polyepoxides having upto 12 or more epoxide groups per molecule may be readily prepared; These polyepoxide polyester compositions as well as their preparation are more fully described in a copending application having Serial No. 503,323, filed April 22, 1955.

Polyepoxide compositions useful in this invention also include the epoxidized unsaturated natural oil acid esters, including the unsaturated vegetable, animal, and fish oil acid esters made by reacting these materials with various oxidizing. agents. .ilheselunsaturated oil acid esters are long-chain aliphatic acidesters containing from about 15 to 22 carbon atoms. These acids may be esterified by simple monohydric alcohols such as methyl, ethyl or decyl alcohol, by polyhydric alcohols such as glycerol, pentaerythritol, polyallyl alcohol, or resinous polyhydric alcohols. Also suitable are "the mixed esters of polycarboxylic acids and long chain unsaturatednatural oil acids with polyhydric alcohols, such as glycerol and pentaerythritol. These epoxidized oil acid esters may contain from more than 1 up to epoxide groups per molecule. The

method of epoxidizing these unsaturated oil acid esters consists of treating them with various oxidizing agents, such as the organic peroxides and the peroxy acids, or with one of the various forms of hydrogen peroxide. 7 A typical procedure practiced in the art consists of using hydrogen peroxide in the presence of: an organic. acid, such as acetic acid, and a catalytic material," such as sulfuric acid. More recently epoxidation methods have consistedof replacing the mineral acid catalyst with a sulfonated cation exchange material, such as the sul-fonated copolymer of styrene divinylbenzene.

The epoxide compositions which may be used in preparing the compositions of this invention also include aliphatic polyepoxides which may be illustrated by the products obtained by polymerizing allyl glycidyl ether through its unsaturated portion.

This reaction may be carried out so as to give higher polymers than the dimer shown. Other aliphatic polyepoxides useful in this inventionmay be illustrated by the poly(epoxyalkyl ethers derived from polyhydric aicohols; These materials may in general beprepared by reacting an a liphatic polyhydric alcohol with an epihalohydrin in the presence of a suitable catalyst and in turn dehydrohalogenating the product to produce the epoxide composition. The production of these epoxides may be illustrated by the reaction of glycerol with epichlorohydrin in the presence of boron trifiuoride followed by dehydrohalogenation with sodium aluminate as follows:

onion 0 BF: 011011 +3 monomer onion t CHzOCHiCEOHCHzCI omoornonorn l t O NaAlC 6\ onoonlonorrornol 01100112 HOE:

. I a 0 omoontononornci moonlonon It is to be understood that such reactions do not give pure compounds, and that the halohydrins formed and the epoxides derived therefrom are of somewhat varied chanacter depending upon the particular reactants, their proportions, reaction time and temperature. In addition to epoxide groups, the epoxide compositions may be characterized by the presence of hydroxyl groupsand halogens. Dehydrohalogenation .aifects only those 11y: droxyl groups and halogens which are attached toadjacent carbon atoms. Some halogens may not be re moved in this step in the event that the proximate carbinol group has been destroyed byreaction-With an epoxide group. These halogens are relatively unreactive, and are not to be considered as functionalgroups in the'conversion of the reaction mixtures of this invention. The preparation of a large number of these mixed polyepoxides is described in the Zech patents, U.S 2,538,072, 2,581,464, and 2,712,000. Still other polyepoxides which have been found to be valuable are such epoxide compositions as diepoxy butane, diglycid ether, and epoxidized polybutadiene. p p p 1 The complex resinous polyepoxides usedliu the" ex amples and illustrative of the commercially prepared products of this. type are the Epon resins marketed by Shell Chemical Corporation. The following table givesthe properties of some Epon resins which are prepared by the condensation in the presence of alkali of bis(4- hydroxyphenyl)isopropylidene with a molar excess of epichlorohydrin in varying amounts.

: l Isasjedon 49 7, hvontn hi butylcaibitol' at 25 0.

describe the. preparation of typical polyepoxide. polyesters.

EX MPLB Breperqtianof polr t from etmhy ropht i n ydride n e hyle y o "In a. 3-neck flask provided with a thermometer, mechanicalagitatorpand a refiuxcondenser attached through a are trap; was placed a mixture of l mols of tetra hydrophthal-ic anhydride -and 2 mols of n-butanol. After. melting the tetrahydrophthalic anhydride in the presence of the butanol, 2 mols. of ethylene glycol were added. The reaction mixture was gradually heated with agitation to 225C. at which point a sufficient amount ofxylene was added to-give' refluxing at esterification temperature. The reaction mixture was then heated with continuous agitation at 225-235 C. until an acid value of 4.2 wa1s obtained. This. product gave an iodine value of 128.

' Epoxidationof the polyester resin In a 3-neck flask provided with a thermometer, a. mechanical agitator, and a reflux condenser was placed 107 parts of the dehydrated acid form of a cation exchange resin (Dowex 50X-8, 50-100 mesh, Dow Chemical Company, a sulfon-ated styrene-divinylbenzene copolymer containing about 8% divinylbenzene, the percent divinylbenzene serving to control the amount of crosslinkage. The Dowex resins are discussed in publications entitled Ion Exchange Res-ins No. 1 and Ion Exchange Resins No. 2, copyrighted 1954 by Dow Chemical Company, the publications having form num- I her Sp32-254 and Sp31354, respectively), and 30 parts glacial acetic acid. The mixture of cation exchange resin and acetic acid was allowed to stand until the resin had completely taken up the acid. To this mixture was added 200. parts of the polyester resin dissolved in an equal weight of xylene. 'To the continuously agitated reaction mixture was added dropwise over a period of 45 minutes to 1 hour 75 parts of hydrogen peroxide. The reaction temperature was held at 60 C. requiring the application of some external heat. (In some preparations involving other polyester resins, 'sufiieient exothermic heat is produced during'the addition of hydrogen peroxide so that no external heat is required, or even some external cooling may be required.) The reaction was continued at 60 C. until a milliliter sample of the reaction mixture analyzed less than 1 milliliter of 0.1 N sodium thiosulfate in an iodometric determination of hydrogen peroxide. The product was then filtered, finally pressing the cation exchange resin filter cake. The acid value of the total resin solution was 4.2. The percent nonvolatile of this solution amounting to 400 parts was 50. This 400 parts of solution was thoroughly mixed with 1 10parts of the dehydrated basic form of Dowex 1 (an anion exchange resin of the quaternary ammonium type, Dowex l is a styrenedivinylbenzene copolymer illustrated by the formula RR N+OH where R rep- 8? sent h st e i r bsnzeae at eeatl R s. methyl group, manufactured by the Dow Chemical Company). The resulting mixture was their filtered-followed by pressing as much of the solution as possible from the anion, exchange resin cake. This product had an acid value of 4.5 and an epoxide equivalent of 288 based on; on nonvolatile resin content of 42.0%. The epoxide values as discussed herein were determined by refluxing -for 30 minutes a Z-gram sample with 50 milliliters of pyridine hydrochloride in excess pyridine. (The pyridine hydrochloride solution was prepared by adding 20 milliliters of concentrated HCl to a liter of pyridine.) After cooling to. room temperature, the. sample is. then back-titrated with standard alcoholic sodium hy.- droxide. i r EXAMPLE 5, p

F l owing t e pro edure fi E amp e 4, polyester-t resinwa pr p r m 5 mols of t t a ydroph ha icane hy i .11.19 8. of o hylene glyc l, nd 2111018. gt-11.11 butanol. 'This product had an acid value of 5.3 and an iodi Value f 0 This; p lye r. r sin was. epox -I di edf n he ma ner pr ou y de c d. 9 ve n ep xi e eq ent ht. 01513.71, ontho Q IYQ Q' HQ'CQIh nt.- he no v at le ntent f this-res n solution as. prepared was 40.2%. a

EXAMPLE 6 The process of Example 4 was followed to obtain a polyester [resin from 1.1 mols of tetrahydrophthalic any ide 1 mo o 4:b t ms1 and 0, ol of n-butanol.

'Thonr uo ad an. ac d .11 1:v o 8,6 Thi'S Polyest r a. Preparation ofaikyd resim-To a kettle provided with. a condenser was added 290' of white refinedso a e l. While u b a n inuous st eam of nitrogen throughthis oil, the temperature was raised to 250 C., at which temperature 0.23 part oflitharge was added andthe temperature held at 250 C, for 5, minutes. While holdi -t e mperat re above :18; 68 parts of technical pentaerythritol was added afterwhich the emao a ur as is dto 2-38 andh ld. until a woo llp fthe produ and. 2 /2 parts ofmethyl l h l how d no ins lubility (about 15;.minutes), Atthis point 136 parts of phthalic anhydridel was. added-and the temperature gradually raised to. 250.? O. andheld. at thistemperature for 30 minutes. At this point the. con: denser was removed from the kettle and the pressure re: duced somewhat by attaching to, a. water aspirator. evacu, ating system. With continuous agitation the. mi'xturewas then held at 250 C. until the acid value had reached 10.5. At this point the resin was thinned. withxylene to 48;%nonv olatile contenthaving aviscosity. of (Gardner bubble viscosimeter). p

b, EpoxidatiOn of a soya bean oil acid modified alkyd resin.- -In' a 3-neck flask provided withv a thermometer,.-a mechanical agitator and a reflux condenser was. placed 70 parts of dehydrated acid form of a cation'exchange resin (Dowex 50X-8) and 15 parts glacial. acetic acid. The mixture of cation exchangeresin and acetic acid was allowedto stand until the resin. had completely taken Blithe acid To. this mixturewas added 3.15 parts of th e alkyd resin solution described in the above paragraph and parts of xylene. To the continuously. agitated reaction mixture. was added dropwise 38 parts of 50% hydrogen peroxide. The reaction temperature. was held at 60 Quntil; a milliliter simple. of 1the.1reaction mixture analyzed less than one milliliter of 0.1 N sodium thio- Admex 710, an epoxidized soya bean oil having an equivalent weight to an epoxide of 263, was dissolved in methylethyI ketone to a nonvolatile content of 50%. Admex 710, a product of the Aircher-Dani els-Midland Company has an acid value of 1, a viscosity of 3.3 stokes at 25 C. and an average molecular weight. of 937.

Examples 9 and 10 describe the preparation of simple aliphatic polyepoxides.

i EXAMPLE 9 In a reaction vessel provided with a mechanical stirrer and external cooling means was placed 276 parts of glycerol and 828 parts of epichlorohydrin. To this reaction mixture was added 1 part of 45% 'boron trifluoride ether solution diluted with 9 parts of ether. The reaction mixture was agitated continuously. The temperature rose to 50 C. over a period of 1 hour and 45 minutes at which time external cooling withice water was applied. The temperature was held between 50 and 75 C. for 1 hour and 20 minutes. To 370 parts of this product in a reaction vessel provided with a mechanical agitator and a reflux condenser was added 900 parts of dioxane and 300 parts of powdered sodium aluminate. With continuous agitation this reaction mixture was gradually heated to 92 C. over a period of 1 hour and 50 minutes, and held at this temperature for 8 hours and 50 minutes. After cooling to room temperature the inorganic material was removed by filtration. The dioxane and low boiling products were removed by heating the filtrate to 205 C. at 20 mm. pressure to give 260 parts of a pale yellow product. The epoxide equivalent of this product was determined by treating a l-gram sample with anexcess of pyridine containing pyridine hydrochloride (made by adding 20 cc, of concentrated hydrochloric acid per liter of pyridine) at the boiling point for 20 minutes and backtitrating the excess pyridine hydrochloride with 0.1 N sodium hydroxide using phenolphthalein as indicator and considering one HC1 as equivalent to one epoxide group. The epoxide equivalent on this product was found to be 152.

EXAMPLE 10 In a -3-neck flask provided with a thermometer, a mechanicalagitator, a refluxcondenser and a dropping funnel was placed 402 parts of allyl glycidyl ether. vWith continuous agitation the temperaturewas raised to 160 C. at which time one part of a solution of methyl ethyl ketone'peroxide dissolved in diethyl phthalate to a 60% content was added. The temperature was held at 160 165 C. for a period of 8 hours, adding one part of the methyl ethyl ketone peroxide solution each minutes during this Show period. After the reaction mixture had stood overnight, the volatile ingredients were removed by vacuum distillation. The distillation was started at 19 mm. pressure and a pot temperature of 26 C. and volatile material finally removed at a pressure of 3 mm. and a pot temperature'of 50 C. The residual product had a molecular weight of 418 and equivalent weight to epoxide content of 198 the yield amounting to 250 parts. Two general classes of aldehyde condensates are contemplated for preparing the modified products of this invention, thoseprepared from ammonia derivatives and r 10 those derived from phenols, with the choice being dependent on the end uses and eharacteristics desired. For instance, if the enduse were to be a white enamelythe ammonia derivative-aldehyde condensates would probably be chosen because of their extremely light initial color and their good color retention, the phenols are somewhat darker in color and have a tendency to yellow upon aging. For the most desirable non-polar solvent solubility, the phenol-aldehyde condensates would be the proper choice since the ammonia derivative-aldehyde condensates usual- ;.1y require some butanol and xylol present to give the desira ble solubility. For certain applications, the butanol odor is objectionable and at times incompatible with the {resin with which it is used. Adhesion to metals also appears to be better in the phenol-aldehyde condensates.

From an economic standpoint, the phenol-aldehyde condensates are advantageous, being lower in price. The aldehyde-ammonia derivative condensation products are formed by the reaction of aldehydes with amines or amides such as urea, thiourea, and their derivatives, melamines and sulfonamides. It is well known that various amines and amides will react with formaldehyde to form aldehyde-amine or aldehyde-amide condensates. A number of derivatives of the amines and amides mentioned are also contemplated herein. Exernplary derivatives are substituted urea, thiourea, or melamine such as the long-chain alkyl substituted materials which impart oil or organic solvent solubility. Suitable sulfonamides include aromatic mononuclear sulfonamides such as toluene sulfonamide, polynuclear sulfonamides such as naphthalene sulfonamide, sulfonarnides of aromatic polyunclearethers and monoor polyf unctio nal sulfonamides. In addition to melamine, other operable ammonia derivatives containing the azide bridge are the amino diand triazines.

. p In the condensation of aldehydes with the organic ammonia derivatives, initially the reaction appears to be the addition of aldehyde to the organic ammonia derivative to .form primarily intermediate alkylol compounds. These compounds will further condense to form more resinous materials, combining with each other through alkylene bridges formed between the nitrogen atoms of the compounds.

I Inthe alkylol condensate, and in the more condensed products of an advanced stage of condensation, there are hydrogen atoms present in the hydroxyl groups which 7 have been formed in the production of the alkylol condensate and which have not been destroyed by further condensation. There are also an appreciable number of hydrogen atoms attached to nitrogen atoms of the amide or. amine groups present in the condensation products. These hydrogens contained in the hydroxyl groups and the amide or amine groups are active with respect to epoxide groups and will react therewith. in the reaction mixtures of this invention to form complex, cross-linked products.

In general, the condensation products of ammonia derivatives and aldehydes contemplated herein are partial and intermediate reaction or condensation products of aldehydes," particularly formaldehyde, with amines or amides, or mixtures thereof. The reactions which pro.- duce such condensation products involve the removal of amino or amido hydrogen atoms from the ammonia derivative. Therefore, it should be understood that an ammonia derivative, in order to be suitable for condensation with an aldehyde must contain at least one hydrogen atom attached to the nitrogen atom. Fusible materials of varying degrees of condensation may be used with the epoxides and theautoesters to form the new composi-. tions and reaction products of this invention. Thus, the condensates may be made by various processes known. in the art for the manufacture of aldehyde-ammonia derivative resins, resulting in water-soluble, alcohol-soluble or Y oil-soluble types. 1 H For use herein, the aldehyde-ammonia derivative can 11 densate y be in its monomeri 'f rm. whieh'i ssentially an alkylol' or pelyalkylol prod r may b highly condensed. It is suitable as long as it is still fusible. and is solublein or compatible with the epoxide composition and the autoester composition with which it isto be reacted.

Many of: the commercial products derived f rom'the reactionjof urea, thiourea, or melamine with formaldehyde. are mixed products, made by reacting the formaldehydewithlmixtures of t ese mat r al S compo or mixed. reaction products'can advantageously be used for. reaction with the epoxides and-the aryloxy acid autoesters according to the present invention. In. addition, many of the present day commercial resins derived from aldehydes and urea, thiourea, or melamine, or a mixture thereof, are prepared in the presence of alcoholic or other solvents which take part in the reaction and become anv integral part of the resulting resin composition. This is illustrated by the. products prepared in the presence of butyl alcohol in which case the butyl alcohol to some extent condenses with the alkylol groups of the aldehyde condensate to give butyl ether residues as a part of the final composition. Such modified products arealsosuitable. In some cases it may be desirable to use v an ammonia derivative-aldehyde condensate which is completely soluble in a, common solvent or a mixture of solvents used to dissolve epoxide and the autoester. Solutions'prepared in this manner can be applied as a coating and the solvent subsequently evaporated before the main reaction between the epoxide, aryloxy acid autoester, and condensate takes place.

. Examples 11 to '15 inclusive describethe preparation of typical ammonia derivative-aldehyde condensates suitable for use herein.

EXAMPLE 11 Ina 3-liter 3-neck flask provided with a mechanical agitator, a thermometer, and reflux condenser was. placed 1 20 parts of urea, 600 parts of 37% aqueous formaldehyde, and 1040 parts of n-butyl'alcohol. With continuous. agitation the reaction mixture was heated to reflux temperature. and the refluxing continued for -a period of 1 hour. At this point a water trap was placed between the reflux condenser and flask and filled with toluene. Distillation was continued until 315 parts of water. were removed from the reaction; mixture. The resulting mixture was. cooled to room temperature, filtered, and 1030 parts of a clean water-white, syrupy liquid isolated.

EXAMPLE 1 The. procedure of preparation including the water removal was. the same as that used in Example 11. A mixture of 304 parts, of thiourea, 960 parts of 37% aqueous formaldehyde, and 800..parts of n-hutyl alcohol was used to give a final 'yield of 1214 parts of a. clear, light amber, syrupy product.

EXAMPLE 13 The procedureof preparation including the removal of water: was the same as that used in Example 11. .A mixture of 120 parts of urea, 148 parts of thiourea, 950 parts of 37% aqueous formaldehyde, and 800 parts. of n-butyl alcohol was used to give a final yield of 1175 parts of a clear, almost colorless syrupy liquid.

EXAMPLE 14 In a 3-liter 3-neck flask provided with a mechanical agitator, a. thermometer, and a reflux condenser was placed: 378 parts of melamine, 840 partsof- 37% aqueous With continuous agitation the reaction mixture was heated. to reflux temperature and'the refluxing continued for a period of 30 minutes, At this point, a water trap was placed; in thedistilling column between the flask and the reflux condenser and filled with toluene. The refluxing was contin ed. untila. ot lof p r s of; wat r-h In a 3-liter 3-neck flask provided with a r'nechanical agitator, a thermometer, and a reflux condenser was placed 1370parts ofp-toluenesulfonamideand 640 parts or 37% aqueous formaldehyde the pH of which had been previously adjusted'to 6.4.0' with potassium acid phthalate and sodium hydroxide. With continuous agitation the reaction mixture Was heated to reflux tempera ture over a period of 40 minutes and the refluxing continued for a period of minutes. At this point the reaction mixture was allowed .tO. cool and the water decanted' from' the resin. The resin was washed 3v times with warm water and finally dehydrated in vacuum at -50 mm. pressure, using a maximum flask temperature of 90 C to yield 1245 parts'of water white resinous solid. i i

The second class of-condensates suitable for modifying the compositions herein described are those which contain reactive phenolic hydroxyl groups, formed by the reaction of phenols and; aldehydes. Phenol and formaldehyde react to form a variety of reaction products, depending upon the proportions. and conditions of reaction. These include. products such as phenol alcohols having both phenolic and alcoholic hydroxyl groups and products of the diphenolmethane typecontaining. phenolic hydroxyl groups only. The condensation of phenoland formaldehyde. can be carried out with the use of acid or' alkaline condensing agents and in some cases. by first combining the aldehydewith an alkali such as ammonia to .form hexamethylenetetramine and reacting the latter with the phenol. The phenol-.aldehyde resinsat an initial or intermediate stage of reaction are intended to be included in the term phenol-aldehyde condensates as. used herein, 1 a

In general, the phenohaldehyde condensates should not have their condensation carried so far as to become insoluble and nonreactive. It is preferred in the preparation of the instant compositions, that they beused at an intermediate stage or at astage of reaction such that they contain reactive phenoliehydroxyl groups or both phenolic and alcoholic hydrbxylg'rohps. This. is desirable in order to permit a, proper blending'ofthte phenol-aldehydecondensatewithfthe polyepoxides and autoesters. for'su-bsequent reaction therewith.

p The phenol-aldehyde condensates may be derived from mononuclear phenols, polynuclear phenols, monohydr'ic phenols, or polyhydric phenols. The criticalrequirement for the condensate is that it be compatible'with the polyepoxides and autoesters orwith-the'tworeactants in a solvent used as a reaction medium. The phenol-alde-v hyde condensate which is essentially a polymethylol phe nol rather than a polymer may be used in the preparation of the new phenol-aldehyde, polyepoxide, autoester condensation products, or it may. be. used: after. furthercom densation, in which case some ofthe methylob groups are usually considered to have. disappeared in the process of condensation. Various so-called phenolic resinswhich result from the reaction. of phenolsand: aldehydes, and particularly from commonphenols or cresols and formal.- dehyde, are available as. commercial products both. of aninitial .andintermediate character. Such. products in: clude resins, which. are readily. soluble in-'common-. sol? vents or readily fusiblesothat they canbe admixed'with the epoxides andj autoesters and reacted therewith to form, the productsof this invention. v

- In selecting a phenQl aldehydecondensate one may choose either the -heatc onve rt;ing or; the 'permanently fus: ibletype. For. example, the formaldehyde reaction prod:

ucts of such phenols; as. carbolic acid, resorcinol, and

bis(4 hydr oxyphenyl-) isopropylidene; readily convert to inu h e n luble mra s t nso fih pn1i a i n;of;heat On; he. e her; nd... o h rare a l yleted Phenols;

as illustrated by p-tertbutylphenol, produce permanently fusible resins on reaction with formaldehyde. Even though fusible condensates are employed, however, insoluble, infusible products result when they are heated in combination with the epoxides and the autoesters described. i

Examples 16 to 18, inclusive, describe the preparation of some of the operable phenol-aldehyde condensates which may be used in combination with the polyepoxides and the 'aryloxy acid autoesters to form the products herein described. i

EXAMPLE l6.

Condensation of Bispher ol [bis(para-hydroxyphenyl) isopropylidenel' with formaldehyde 1 i In a 3-liter, 3-neck flask provided with a mechanical agitator, a thermometer, and a reflux condenser was placed 912 parts of Bisphenol A, 960 parts of 37% aque ous formaldehyde,-and 2.3 parts of oxalic acid. With continuous agitation, the reaction mixture was heated to the reflux temperatureand refluxing continued for a period of 1 hour. After permitting the reaction mixture to cool to around 50 C. the water layer was removed by decantation. The phenol-formaldehydelayer was then washed three times with waterwhich in'each casewas removed by decantation. The last portion of water was removed by distillation at reduced'pressure using a-water aspirator system which gave pressure around 3040mm. The temperature during the removal of this last portion of water ranged from 70-90 C. The product, amountweight basis range up to about 70%, but from a practical standpoint, the preferred percentage is about 10%.

Compositions containing the polyepoxides and the autoesteror such compositions modified with aldehyde condensates may be used as mixtures or at varying intermediate stages of reaction. The initial mixtures or intermediate reaction products which are soluble in common organic solvents may be blended in solution in proper proportions and the solutions then applied as an impregnant for fabrics or paper, or for the formation of protective coating films. Subsequent heating functions to remove the solvent and bring about polymerization to the insoluble, infusible state. For other uses, the'initial or intermediate mixture may be used together without a solvent, giving directly a composition which, on the application of heat, converts to an infusible, insoluble final product. i i i i For the preparation of semi-liquid adhesive compositions, low-melting or syrupy polyepoxides would be used with a low-melting autoester or autoester and aldehyde condensate. For various other applications, higher melting compositions are desirable in which case: partially polymerized mixtures of the polyepoxide and the autoester could advantageously be used. An alternative method of obtaining the higher melting compositions is to choose 1 higher melting forms of the polyepoxide and autoester.

In making the new compositions and products herein described, the polyepoxides and the autoester or such ing to 1065 parts, was a clear, heavy, syrupy material.

. EXAMPLE 17 1 Reaction of p-tert iqry butylphenol with -f0rrhaldehyde The procedure of. preparation, including the dehydracompositions modified with aldehyde condensates may be used in regulated proportions without the addition of other materials. For certain uses, other components are often advantageously added, including filling and compounding materials, plasticizers, pigments, etc. Compositions which tend to give somewhat brittle products on conversion to pounded with plasticizers.

tion step, was the same as that used in Example 16. A. mixture of 1000 parts of p-tert-butylphenol, 1067 parts of 37% aqueous formaldehyde, and 10 parts of sodium hydroxide was usedto give a final yield of 1470 parts of a clear, almost colorless syrupy product.

EXAMPLE 1s a Reaction of phenol with formaldehyde Again a reaction procedure includingthe dehydration step was the same as that used in Example 16. A mix-, ture of 658 parts of phenol, 1400 parts of 37% aqueous formaldehyde, and .6.6 parts of sodiumhydroxide was. used to give a final yield of 1168parts of a clear, syrupy product. 1 I

In making the new'compositions, the polyepoxide and autoester or such compositions modified with aldehyde condensates are admixed in suitable proportions and re-' action will proceed merely by the application of heat. More specifically the reaction is effected byQheating the mixtures at elevated temperatures, usually in the range of about 100-250" C. Catalysts are unnecessary, but in certain cases it may be desirable to speed up the rea tion by the use of catalysts, such as boron trifluon'de adi ducts, sodium phenoxides, and mineral acid type catalysts. The reaction mixtures andfinal reaction products of this invention may be preparedby using varying ratios of epoxide to autoester. The quantities of reactants em: ployed in a given instance will depend upon the characteristics desired in the final product. Flexibleconversion products can be obtained from ahardjepoxide by employing relatively large amounts ofa low-melting autof,

the insoluble, infusible state are advantageously com- For most applications, however, it is possible. to obtain suitable flexibility and toughness by regulating the proportions and types of reacting ingredients, thereby obviating the need. for plasticizers.

The application of heat to the mixtures herein set forth may involve several chemical reactions. It will be appreciated that the reactions involved are very complex and the extent to which each takes place will vary with the temperature used in heat treating, the period of time .j aldehyde condensate, if used, and autoester chosen. While it is not desired to be limited by any theoretical explanation of the exact nature of these reactions, it seems probable that conversion to the final polymeric products is accompanied by direct polymerization of the -epoxide groups inter se; reaction of the epoxide groups with methylol hydroxyl groups; reaction of the epoxide 1 groups with phenolic hydroxyl groups, and reaction of epoxide groups with active hydrogen attached to a nitrogen atom, all of which take place to some extent simultaneously in forming the final products.

The present invention provides a wide range of reaction compositions and products including initial mixtures reaction products as well as final reaction products.

ester or a low-melting autoester and a low-melting phev nol-aldehyde condensate orfiexibility maybe imparted by largeramounts of a soft epoxide; In general, operable ing from 2:1 to 1:2] In instances where an aldehyde con densate is used as a modifier, operable amounts on a products are those in which the ratio of epoxideto auto" alkali, acids, and organic solvents.

of the polyepoxides, aldehyde condensates, and the autoesters, partial or intermediate reaction products of such mixtures and compositions containing such intermediate In general, the initial mixtures, as well as the intermediate reaction products unless too highly polymerized, are soluble in solvents of the lacquer type, such as ketone or ester solvents.

In addition to having outstanding physical properties, such as hardness, toughness, and flexibility, the final infusible, insoluble products have outstanding chemical properties, such as high resistance to oxidation, water, It has also been observed that the final conversion products possess unusually good adhesion to most surfaces including metal,

I glass, wood, and plastics.

This property of outstanding adhesion to a wide variety of surfaces gives the subject which they were prenv M L l 4 4 2 /0 z 4 4 0 4.

m wmmm mmmmmmmmmmmmmm 341.12 1 14a 7 imasn mmmmmmmmmm 4mg 8 s s msesma m m 888888 888888888888BS W SBSSSM MSS888BU MWW S88888 888 88668 88 888%82%W H m a mm mmmm uwmmmmmmmmwmm Md WWWW WWWW 8M 3333 3364 Mixtures of the resinous Parts of aldehyde condensate m1n./ U.

6 Ex, 11--- 0 Ex. 12.-- 7 EX. 13.--

The epoxi ized polyesters. were used at the Proportions as usedinthe following table refer coating films, each of the. autoesters and the polyepoxides with the exception of epoxidized polyesters 'were' dissolved in methyl ethyl ketone to a nonvolatile content of 40-60%.

pared. The aldehyde condensates were dissolvedin a mixture of methyl ethyl ketone and butanol to a nonvolatile content of 40-60%.

autoester and polyepoxides or such compositions modified with aldehyde condensates were found to be stable for extended periods of time at normal temperatures. Mixtures of the solutions were spread on panels with a .002 Bird applicator and the'films were baked for periods of 30 to'90 minutes at temperatures ranging from 175- 250 C.

to parts by weight and are based on the nonvolatile content of the solutions of reactants.

ion ive m r m 3 2312312313113231223 3123 2321 s S8 XXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX Y. E EEXXXX nu m nnnnnjaesnn n finnnnnn n jnnnnnnnnjjaaadaaaassnn 55555222255i5=m8555555&6815555555.08111111 118155 4 4 4 1 7 7 H 4f n 4 .m mmmmmmmmmr fiwm 06 p mm1111 111% 811 m8 m nnnnnnn nnn n x OOOOOOOOOHHOOO 0 S0 pppppppmmppp p w E EEEEE EEE n a .n .en 3 P &a flmuflwa wm ing a formu- Ex. No.

in formulat infusible state, 5 nonvolatile and in the solvent in the insoluble,

In the preparat 15 products high potential value for use hesives.

This property is also of extreme value in lating protective coating films for use on many types of surfaces. The adhesion characteristics are probably due to the fact that even in the converted, the compositions contain a relatively high percentage of highly polar groups, such as ether groups, ester groups, and alcoholic and phenolic hydroxyl groups. Despite the hi h percentage of polar groups fusible products of this inventionthe tolerance for water 10 is unusually low, apparently due tothe high molecular weight and rigid cross-linked structure of the final compositions. Examples 19 to 151, inclusive, illustrate the preparation of insoluble, infusible protective coating films from 15 the compositions of this invention. of the composition for heat curing to form the protect Films resistance Parts of poly- Parts of in- Parts of Baking X. N epoxide terester aldehyde schedule, aquecondensate min/" :0 Boiling 011s water, hr. NaOH .at 0., hr.

95 8.3 Ex. 7 5.0 Ex.1.... 1.3 D-X. 1 .8 9 8. 0 EX. 7.. 1:0 EX. 3. 1:0 Ex. 3% 2% 97 2.5 EX. 2.5 Ex. 3.... 5.0 Ex. 96 /4 1.0-EX. 8 1.0 EXMB. 8.0 EX. ,6 A 6.7LE-X. 10.0 E11... 1.7 8 5L9'EX.9 10.0 Ex. 2. 1.6 EX. 8 27 5.1 EX. 10.0 Ex. 1. 1.5 EX. 8 27 9.5 EX. 10.0 EX. .3. 2.0 EX. 8 4 2 9.5 EX. 9 .10.() Ex. 3. 2.0 EX. 8 ,6 12:6 EX. 10 10.0 EXrB.-. 2.3 EX. 4% 12 6.7 EX. 10.0.Ex. 1.-- 17. Ex. .8 32 110 EX 8.0Ex. 1 1.0 EX. -34 '8 2.0.EX .3.0 Er 5.0 Ex. /4 1 .32 1.0 EX. 1.0 E 8.0 EX. =68 4.4 EX. 5.0 Ex. 0.9 Ex. 2 4% 8.3 EX. 5.0 EX. 1.3 EX. 8 6 9.6 EX. 5.0 Ex. 1.5 EX. 1% 4% 8.2 EX. 8....-. 5.0 EX. 3 1.3 EX. 8 16 15.5 Ex. 7.-. 5.0 EX. 3 2.1 EX. 2 1 8.3 Ex.7.......- 5.0EX.1-- 1.3 EX. M2 /0 115. 4.8 EX. 4 5.0 EX. 1...- 1.0 EX. 8 8 116. 6.4 Ex. 5 5.0 Ex. 2.... 1.1 Ex. 8 6 117. 5.6 EX. 6 5.0 EX. 2.. 1.1 EX. 8 30 118..- 10.4 EX. 5 5.0 EX. 3.-.. 1.5 EX. 8 $6 119 9.0 Ex. 4 5.0 EX. 3..-. 1.4 EX. 4% 32 120 6.4 EX. 5. 5.0 EX. 2...- 1.1 EX. 4% 1 121..-- 8.0 EX. 5-...---. 1.5 EX. 3.--. 1.0 EX. 2% 16 122 1.0 EX. 5 8.0 EX. 2..-. 1.0 EX. 5 123- 2.5 EX. 5...-. 2.5 EX. 3.-.. 5.0 EX. V4 V4 124. 1.0 Ex. 1.0 EX. 3.-.. 8.0 EX. 16 $4 125. 8.1 Epon 1001- 5.0 EX. 1.... 1.3 EX. 8 168 126. 14.8 Epon 1007. 2.5 EX. 1... 1.8 EX. 8 168 127. 5.6 Epon 864.. 5.0 EX.1... 1.1 EX. 8 168 128. 15.0 Epon 1001. 5.0 Ex. 3..-. 2.0 EX. 8 68 129. 17.2 Epon 1004-. 5.0 EX. 2-..- 2.3 EX. 8 168 14.0 Epon 1004.. 2.5 Ex. 3..-- 1.7 EX; 8 168 17.0 Epon 1007- 2.5 EX. 2.... 2.0 Ex. 8 168 10.5 Epon 864.. 5.0 Ex. 3.. 1.6 EX. 8 168 15.0 Epon 1001. 5.0 EX. 3.. 2.0 EX. 8 168 14 9 Epon 1004 5.0 Ex. 1--.. 2.0 EX. 8 168 1 0 Epon 864.-.. 8.0 EX. 2.--. 1.0 EX. 5

.5 Epon 864.--- 2.5 EX.3..-- 5.0 EX. $4 .0 Epon 864.... 1.0 Ex. 3..-. 8.0 EX. 16 V1 .0 Ex. 7.. 1.0 Ex. 3---. 1.0 EX. /4 1e .0 EX. 8. 8.0 Ex. 2. 1.0 Ex. 8 .5 Ex. 8.- 2.5 EX.3.... 5.0 Ex. is A .0 Ex. 8.- 1.0 Ex. 3-. 8.0 Ex. 16 A .1 EX. 9.. 10.0 EX. 1. 1.5 EX. 8 12 5.9 EX. 9.. 10.0 EX. 2. 1.6 EX. 8 30 7.8 EX. 10.- 10.0 EX. 2. 1.8 EX. 8 168 7.8 EX. 10 10.0 EX. 2... 1.8 EX. 8 30 12.6 EX. 10. 10.0 EX. 3. 2.3 EX. 8 6 5.9 EX. 9- 10.0 EX. 2... 1.6 EX. 5% 7 8.0 EX. 10 1.0 EX. 3.-.. 1.0 EX. 2% A2 1.0 Ex. 0. 8.0 EX. 2.-. 1.0 Ex. 5 2.5 EX. 9. 2.5 EX. 3.... 5.0 EX. 92 1.0 Ex. 0.. 1.0 Ex. 3.... 8.0 EX. $4

1 .02 part NaOEt catalyst was added.

It should be appreciated that while there are above disclosed but a limited number of embodiments of this invention, it is possible to produce still other embodiments without departing from the inventive concept here in disclosed.

It is claimed and desired to secure by Letters Patent:

1. A new composition of matter comprising the insoluble, infusible reaction product obtained by heating (A) a resinous polyhydric phenol comprising a self-ester of a pentanoic acid consisting essentially of 4,4-bis(4- hydroXyaryDpentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1-5 carbon atoms and (B) an organic polyepoxide containing an average of more than one oXirane group per molecule and being free of groups reactive with said self-ester (A) other than hydroxyl, carbonyl and oXirane.

2. The composition as described in claim 1 wherein (A) is a resinous polyhydric phenol comprising a selfester of a pentanoic acid consisting essentially of 4,4-bis- (4-hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of one carbon atom.

3. The composition as described in claim 1 wherein (A) is a resinous polyhydric phenol comprising a selfester of a pentanoic acid consisting essentially of 4,4- bis(4-hydroxyphenyl)pentanoic acid.

4. The composition as described in claim 3 wherein (B) is a complex resinous epoxide which is a polymeric polyhydric alcohol having aromatic nuclei united through ether oxygen and terminating in oxirane substituted chains.

5. The composition as described in claim 3 wherein (B) is a polyepoxide polyester of tetrahydrophthalic' acid and a glycol, wherein the epoxy oxygen bridges adjacent carbon atoms-on the tetrahydrophthalic acid residue.

6. The composition as described in claim 3 wherein (B) is an aliphatic polyepoxide, said polyepoxide having only hydroxyl substituents in addition to oxirane groups.

7. A new composition of matter comprising the insoluble, infusible reaction product obtained by heating (A) a resinous polyh-ydric phenol comprising a self-ester of a pentanoic acid consisting essentially of 4,4-bis(4 hydroxyaryhpentanoic acid whereinthe hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1-5 carbon atoms; (B) up to about 70% by weight of a fusible condensation product of formaldehyde and a member of the group consisting of phenol and an organic ammonia derivative, said ammonia derivative being at least one member of the group consisting of urea, thiourea, melamine, p-toluenesulfonamide and alkyl derivatives thereof and (C) an organic polyepoxide containing an average of more than one oXirane group per molecule 19 and being free of groups reactive with said self-ester (A) and said condensate (B) other than hydroxyl, carboXyl, and oxirane.

8. The composition as described in claim 7 wherein (A) is a resinous polyhydric phenol comprising a self- 1 (C) is a polyepoxide polyester of tetrahydrophthalic acid ester of a pentanoic acid consisting essentially of 4,4-bis- (4-hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of one carbon atom.

9. The composition as described in claim 7 wherein (A) is a resinous polyhydric phenol comprising a selfester of 4,4-bis(4-hydroxyphenyl)pentanoic acid.

10. The composition as described in claim 9 wherein (C) is a complex resinous epoxide which is a polymeric polyhydric alcohol having aromatic nuceli united through ether oxygen and terminating in oxirane substituted chains.

and a glycol, wherein the epoxy oxygen bridges adjacent carbon atoms on the tetrahydrophthalic acid residue.

12.'The composition as described in claim 9 wherein (C) is an aliphatic polyepoxide, said polyepoxide having only hydroxyl substituents in addition to oXirane groups;

13. The composition as described in claim 9 wherein (B) is up to about 20% by weight of the fusible conden sation product of formaldehyde and at least one organic ammonia derivative of the group consisting of urea, thiourea, melamine, p-toluenesulfonamide and alkyl sub stituted derivatives thereof.

14. The composition as described in claim 9 wherein (B) is up to about 30% by weight of the fusible condensation product of formaldehyde and a phenol. i

No references cited.

UNITED STATES PATENT OFFICE Certificate of Correction Patent N 0. 2,907,727

Sylvan O. Greenlee It is hereby certified that error appears in the numbered patent re as corrected below.

Column 2, Formula I,

the upper right-hand portion thereof should appear as shown below instead of as in the patent:

said Letters Patent should read A +n(om i 2o 4, Formula IV, the rightof as in the patent:

columns 3 and hand portion thereof should appear as shown below instead column 6, Equation VII, the right-hand portion thereof should appear as shown below i s ead of in the patent CHZOCHZ HO CHzCH H2 CH20 GHzCHOHz column 12, line 9, for the numeral 64.0 read sixth column thereof -6.0-; columns 15 and 16, in the table, opposite Ex. No. 62 in the table, fourth for 1% read columns 17 and 18,

column thereof, opposite EX. No. 105 for 17. Ex. 13 read -1.7 Ex. 13; same table, fifth column thereof, opposite EX. No. 127 for 30/209 read -30/200.

Signed and sealed this 2nd day of August 1960.

[sEAiJ Attest .KARL H. AXLINE,

ROBERT C. WATSON, Attestz'ng Ofii'cer.

filo miesioner of Patents.

October 6, 1959 l printed specification of the above quiring correction and that the 

1. A NEW COMPOSITION OF MATTER COMPRISING THE INSOLUBLE, INFUSIBLE REAFTION PRODUCT OBTAINED BY HATING (A) A RESINOUS POLYHYDRIC PHENOL COMPRSING A SELF-ESTER OF A PENTANIOC ACID CONSISTING ESSENTIALLY OF 4,4-BIS(4HYDROXYARYL) PENTANIOC ACID WHEREIN THE HYDROXYARYL RADICAL IS A HYDROXYPHENYL RADICAL AND IS FREE FROM SUBSTITUENTS OTHER THAN ALKYL GROUPS OF FROM 1-5 CARBON ATOMS AND (B) AN ORGANIC POLYEPOXIDE CONTAINING AN AVERAGE OF MORE THAN ONE OXIRANE GROUP PER MOLECULE AND BEING FREE OF GROUPS REACTIVE WITH SAID SELF-ESTER (A) OTHER THAN HYDROXYL, CARBOXYL AND OXITANE.
 7. A NEW COMPOSISTION OF MATTER COMPRISING THE IMSOLUBLE, INFUSIBLE REACTION PRODUCT ONTAINED BY HEATING (A) A ARESINOUS POLYHYDRIC PHENOL COMPRISING A SELF-ESTER OF A PENTANIOC ACID CONSISTING ESSENTIALLY OF 4,4-BIS(4HYDROXYARYL) PENTANIOC ACID WHEREIN THE HYDROXYARYL RADICAL IS A HYDROXYPHENYL RADICAL AND IS FREE FROM SUBSTITUENTS OTHER THAN ALKYL AGROUPS OF FROM 1-5 CARBON ATOMS; (B) UP TO ABOUT 70% BY WEIGHT OF A FUSIBLE CONDENSATION PRODUCT OF FORMALDEHYDE AND A MEMBER OF THE GROUP CONSISTING OF PHENOL AND AN ORGANIC AMMONIA DERIVATIVE, SAID AMMONIA DERIVATIVE BEING AT LEAST ONE MEMBER OF THE GROUP CONSISTING O FUREA, THIOUREA, MELAMINE, P-TOLUENESULFONAMIDE AND ALKYL DERIVATIVES THEREOF AND (C) AN ORGANIC POLYEPOXIDE CONTAINING AN AVERAGE OF MORE THAN ONE OXIRANE GROUP PER MOLECULE AND BEING FREE OF GROUPS REACTIVE WITH SAID SELF-ESTER (A) AND SAID CONDENSATE (B) OTHER THAN HYDROXYL, CARBOXYL, AND OXIRANE. 